EP2077989A1 - Method for producing electronic grade 2,2'-aminoethoxyethanol - Google Patents

Method for producing electronic grade 2,2'-aminoethoxyethanol

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Publication number
EP2077989A1
EP2077989A1 EP07820444A EP07820444A EP2077989A1 EP 2077989 A1 EP2077989 A1 EP 2077989A1 EP 07820444 A EP07820444 A EP 07820444A EP 07820444 A EP07820444 A EP 07820444A EP 2077989 A1 EP2077989 A1 EP 2077989A1
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Prior art keywords
aminoethoxyethanol
stream
crude
filter
diethylene glycol
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EP07820444A
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German (de)
French (fr)
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EP2077989B1 (en
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Helmut Schmidtke
Martin Rudloff
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

Definitions

  • the invention relates to a process for the preparation of 2,2'-aminoethoxyethanol (hereinafter abbreviated to ADG) in electronic quality.
  • ADG is prepared by reacting diethylene glycol with ammonia in the presence of a catalyst. This morpholine is formed as a byproduct.
  • the reaction mixture is usually separated by distillation in several stages, wherein after separation of ammonia ak, water and secondary components of an ADG and a morpholine-containing stream are recovered.
  • the purifying distillation of the ADG-containing stream takes place in a sidestream column in which low-boiling secondary components are removed overhead and high-boiling secondary components are discharged in the column bottom.
  • ADG ADG content of at least 98.0 wt .-%.
  • the apparatuses in the plant for the production of pure ADG (in particular reactors and separation columns) generally consist of austenitic stainless steels, in particular with the material numbers 1.4541 and 1.4571.
  • ADG content min. 98.00% by weight, diethylene glycol content: max. 0.40% by weight, water content: max. 0.20% by weight (determination method Karl Fischer according to DIN 51777), color number max. 20 APHA (according to DIN EN 1557), a maximum content of aluminum, arsenic, gold, boron, calcium, cadmium, cobalt, chromium, copper, potassium, magnesium, manganese, nickel, antimony, tin and titanium of 20 ppb each and a maximum Content of iron, sodium and zinc of 30 ppb each, determined in accordance with ICP-MS (
  • the solution consists in a process for the production of electronic quality ADG by reacting diethylene glycol with ammonia in a reactor in the presence of a catalyst to obtain a reaction mixture, from which a crude 2,2'-ADG stream is separated in a Pure column is further purified by distillation, which is characterized in that a side stream is withdrawn from the pure column, containing ADG in electronic quality by the diethylene glycol is passed before supplying it to the reactor via a filter suitable for solid particles having a maximum particle size of ⁇ 1, 5 microns ensures a separation efficiency of at least 99%.
  • the feed of the diethylene glycol to the production plant can be pre-contaminated in particular by upstream production steps, storage and transport with metal ions, typically with impurities in a concentration of up to 2000 ⁇ g / l or even 400 ⁇ g / l or even 0 to 100 ⁇ g / l.
  • the inventors have recognized that a significant improvement in the residual content of components harmful to specifications, in particular cations, in the ADG is possible if a high-performance filter is installed in the feed line of the diethylene glycol to the reactor, which is used to separate solid particles having a maximum particle size ⁇ 1.5 ⁇ m, preferably with a maximum particle size ⁇ 1 ⁇ m, is suitable.
  • a separation efficiency of at least 60% is achieved, for solid particles with a maximum particle size of 0.6 ⁇ m a separation efficiency of at least 90%, for solid particles with a maximum particle size of 0, 8 ⁇ m a degree of separation of at least 95%, for solid particles with a maximum particle size of 1, 5 ⁇ m a separation efficiency of at least 99% and for solid particles with a maximum particle size of 5.0 ⁇ m a separation efficiency of at least 99.98%.
  • the maximum particle size can be determined, for example, by means of static light scattering.
  • the preferred filter is a bag filter made of polypropylene, in particular with a volume of 30 to 40 l, in particular 32 l, which is used in a separating vessel and flows through from top to bottom. The retention of the impurities takes place on the inside of the filter.
  • the column used for ADG purification by distillation which is arranged at the end of the process chain.
  • the distilled ADG is separated in electronic quality in the liquid state as a side stream, while the organic secondary components having a boiling point> 235 ° C (at 1, 013 bar) in the bottom and the organic compounds having a boiling point ⁇ 222 ° C ( at 1, 013 bar) are discharged from the top of the column.
  • the column is preferably operated at a pressure of 0.005 to 0.2 bar.
  • the feed point of the ADG-containing stream is - based on the theoretical separation stages - above the middle of the column.
  • the opposite liquid side draw of the pure product is 1 to 30, in special cases 10 to 25 theoretical plates above the feed point in the enrichment section of the column.
  • the separation stages which are between the feed of the raw ADG stream and the withdrawal of the side stream containing ADG in electronic quality, compared to known methods, preferably with increased liquid load w L operated (with otherwise constant Speed of rising steam).
  • the liquid load W L represents the ratio between the volume flow of the liquid V L trickling down to the separation stages and the free cross-sectional area A of the separation stages.
  • the liquid load w L has the dimension of a velocity
  • the metallic impurities introduced in the educt of the production plants and present at the feed of the pure column in relatively high proportions could be at an increased ratio of liquid load w L to steam velocity w D , preferably from
  • the process is particularly preferably operated with recirculation:
  • the diethylene glycol which has not been converted into a product of value in the process is withdrawn from the bottoms of the ADG pure column and mixed with the fresh starting material stream containing crude ADG in front of the filter.
  • This process circuit allows an increased discharge of metallic contaminants, especially after shutdown of the system, in which additional impurities are entered into the otherwise closed system by opening system components.
  • the inventive method was used under the conditions mentioned in continuous operation in a production plant.
  • An ADG-pure column with 44 theoretical plates was used, whereby 9 theoretical plates were arranged between the supply of the starting material stream, containing crude ADG, and the withdrawal of the side stream, containing pure ADG in electronic quality.
  • the ratio of liquid loading and vapor velocity was varied for the theoretical plates between the feed of the reactant stream and the withdrawal of the side stream and its influence and the influence of the use of a filter in Eduktweg on the residual iron concentration in the product examined.
  • the ratio of liquid load to vapor velocity was set to a value of 0.165.
  • the process was operated without mechanical filter in the educt path.
  • the product stream containing pure ADG had an iron concentration of 50 ppb.
  • Example 2 The process was carried out analogously to Example 1, likewise without mechanical filter in the educt path, but with a ratio of liquid load to vapor velocity of 0.185.
  • the residual iron concentration in the ADG product stream was 27 ppb.
  • a separation efficiency of at least 60% for solid particles with a maximum particle size of 0.6 ⁇ m a separation efficiency of 90%, for solid particles with a maximum particle size of 0.8 ⁇ m a separation efficiency of at least 95%, for solid particles with a maximum particle size of 1.5 ⁇ m, a separation efficiency of at least 99% and for solid particles with a maximum particle size of 5.0 ⁇ m a separation rate of at least 99.98%.
  • the concentration of iron in the pure ADG in this case was 9 ppb.
  • Examples 4 to 6 were carried out with an iron concentration in the reactant stream of 345 ppb. In each of Examples 4 to 6, a mechanical high-performance filter in the educt path, as described in Example 3 above, was used in each case. Examples 4 to 6 differ by different values for the ratio of liquid load and steam velocity with otherwise unchanged operating conditions
  • the ratio of liquid load to vapor velocity was 0.178.
  • a residual iron concentration in the pure ADG of 7 ppb was achieved.
  • the ratio of liquid load to vapor velocity was 0.155, according to the prior art operation.
  • the ratio of liquid load to vapor velocity was set at 0.175.
  • the residual contamination in the pure ADG stream of iron was 8 ppb.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for preparing electronics-grade 2,2′-aminoethyoxyethanol by reacting diethylene glycol with ammonia in the presence of a catalyst in a reactor to give a reaction mixture from which a crude 2,2′-aminoethoxyethanol stream is separated off and is purified further by distillation in a pure column, wherein a sidestream comprising electronics-grade 2,2′-aminoethoxyethanol is taken off from the pure column as a result of the diethylene glycol being passed through a filter which ensures a degree of removal of at least 99% for solid particles having a maximum particle size of ≰1.5 μm before the diethylene glycol is fed into the reactor, is proposed.

Description

Verfahren zur Herstellung von 2,2'-Aminoethoxyethanol in Elektronik-Qualität Process for the preparation of electronic grade 2,2'-aminoethoxyethanol
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von 2,2'-Aminoethoxyethanol (im Folgenden abgekürzt mit ADG bezeichnet) in Elektronik-Qualität. ADG wird durch Umsetzung von Diethylenglykol mit Ammoniak in Gegenwart eines Katalysators hergestellt. Dabei entsteht Morpholin als Koppelprodukt. Das Reaktionsgemisch wird in der Regel destillativ in mehreren Stufen aufgetrennt, wobei nach Abtrennung von Ammoni- ak, Wasser und Nebenkomponenten ein ADG sowie ein Morpholin enthaltender Strom gewonnen werden.The invention relates to a process for the preparation of 2,2'-aminoethoxyethanol (hereinafter abbreviated to ADG) in electronic quality. ADG is prepared by reacting diethylene glycol with ammonia in the presence of a catalyst. This morpholine is formed as a byproduct. The reaction mixture is usually separated by distillation in several stages, wherein after separation of ammonia ak, water and secondary components of an ADG and a morpholine-containing stream are recovered.
Die Reindestillation des ADG-haltigen Stromes erfolgt in einer Seitenstromkolonne, in der leichtsiedende Nebenkomponenten über Kopf abgetrennt und schwersiedende Nebenkomponenten im Kolonnensumpf ausgetragen werden. Als Seitenstrom wird Rein-ADG mit einem ADG-Gehalt von mindestens 98,0 Gew.-% erhalten.The purifying distillation of the ADG-containing stream takes place in a sidestream column in which low-boiling secondary components are removed overhead and high-boiling secondary components are discharged in the column bottom. As a side stream pure ADG is obtained with an ADG content of at least 98.0 wt .-%.
Die Apparate in der Anlage zur Gewinnung von Rein-ADG (insbesondere Reaktoren und Trennkolonnen) bestehen in der Regel aus austenitischen Edelstahlen, insbeson- dere mit den Werkstoffnummern 1.4541 und Nr. 1.4571.The apparatuses in the plant for the production of pure ADG (in particular reactors and separation columns) generally consist of austenitic stainless steels, in particular with the material numbers 1.4541 and 1.4571.
Für Elektronik-Anwendungen, beispielsweise zum Reinigen von Leiterplatten, werden jedoch an Rein-ADG spezielle Spezifikationsanforderungen bezüglich der zulässigen Restgehalte an Metallen gestellt. ADG in Elektronik-Qualität muss typischerweise die folgenden Spezifikationsanforderungen erfüllen:However, for electronic applications, for example for cleaning printed circuit boards, Rein-ADG has specific specification requirements regarding the permissible residual contents of metals. Electronic grade ADG typically must meet the following specification requirements:
ADG-Gehalt: min. 98,00 Gew.-%, Diethylenglykol-Gehalt: max. 0,40 Gew.-%, Wasser- Gehalt: max. 0,20 Gew.-% (Bestimmungsmethode Karl Fischer nach DIN 51777), Farbzahl max. 20 APHA (nach DIN EN 1557), ein Maximalgehalt an Aluminium, Arsen, Gold, Bor, Calcium, Cadmium, Cobalt, Chrom, Kupfer, Kalium, Magnesium, Mangan, Nickel, Antimon, Zinn und Titan von jeweils 20 ppb sowie ein Maximal-Gehalt an Eisen, Natrium und Zink von jeweils 30 ppb, jeweils bestimmt nach ICP-MS (|on coupled pjas- ma-mass spectrometry).ADG content: min. 98.00% by weight, diethylene glycol content: max. 0.40% by weight, water content: max. 0.20% by weight (determination method Karl Fischer according to DIN 51777), color number max. 20 APHA (according to DIN EN 1557), a maximum content of aluminum, arsenic, gold, boron, calcium, cadmium, cobalt, chromium, copper, potassium, magnesium, manganese, nickel, antimony, tin and titanium of 20 ppb each and a maximum Content of iron, sodium and zinc of 30 ppb each, determined in accordance with ICP-MS (| on coupled Pjasmma mass spectrometry).
Es wurde jedoch gefunden, dass bei der Produktion von ADG unter gewöhnlichen Prozessbedingungen die obigen Spezifikationsanforderungen nicht zuverlässig erreicht werden können. Besondere Einschränkungen bestehen bei der Verarbeitung von Diethylenglykol, welches - beispielsweise durch Lagerung und Transport - mit mehr als 50 ppb durch die oben genannten Metallionen vorverunreinigt ist. Es war daher Aufgabe der Erfindung, ein Verfahren zur Verfügung zu stellen, wonach ADG in Elektronik-Qualität in bestehenden Anlagen gewonnen werden kann, ohne umfangreiche, kostenaufwändige apparative und/oder verfahrenstechnische Zusatzmaßnahmen. Insbesondere sollten keine Änderungen bei der Umsetzung des Eduktes am Katalysator und den zwischengeschalteten Destillationsstufen vorgenommen werden müssen.However, it has been found that in the production of ADG under ordinary process conditions, the above specification requirements can not be reliably achieved. Particular limitations exist in the processing of diethylene glycol, which is pre-contaminated with more than 50 ppb by the abovementioned metal ions, for example by storage and transport. It was therefore an object of the invention to provide a method according to which ADG in electronic quality can be obtained in existing systems, without extensive, expensive apparatus and / or procedural additional measures. In particular, no changes should be made in the reaction of the educt on the catalyst and the intermediate distillation stages.
Die Lösung besteht in einem Verfahren zur Herstellung von ADG in Elektronik-Qualität durch Umsetzung von Diethylenglykol mit Ammoniak in einem Reaktor in Gegenwart eines Katalysators unter Erhalt eines Reaktionsgemisches, woraus ein Roh-2,2'-ADG- Strom abtrennt wird, der in einer Reinkolonne weiter destillativ gereinigt wird, das dadurch gekennzeichnet ist, dass aus der Reinkolonne ein Seitenstrom abgezogen wird, enthaltend ADG in Elektronik-Qualität, indem das Diethylenglykol vor der Zuführung desselben zum Reaktor über einen Filter geleitet wird, der für Feststoffpartikel mit einer maximalen Partikelgröße von < 1 ,5 μm einen Abscheidegrad von mindestens 99 % gewährleistet.The solution consists in a process for the production of electronic quality ADG by reacting diethylene glycol with ammonia in a reactor in the presence of a catalyst to obtain a reaction mixture, from which a crude 2,2'-ADG stream is separated in a Pure column is further purified by distillation, which is characterized in that a side stream is withdrawn from the pure column, containing ADG in electronic quality by the diethylene glycol is passed before supplying it to the reactor via a filter suitable for solid particles having a maximum particle size of <1, 5 microns ensures a separation efficiency of at least 99%.
Der Zulauf des Diethylenglykols zur Produktionsanlage kann insbesondere durch vorgelagerte Produktionsschritte, Lagerung und Transport mit Metallionen vorverunreinigt sein, typischerweise mit Verunreinigungen in einer Konzentration von bis zu 2000 μg/l, oder auch 400 μg/l oder auch 0 bis 100 μg/l.The feed of the diethylene glycol to the production plant can be pre-contaminated in particular by upstream production steps, storage and transport with metal ions, typically with impurities in a concentration of up to 2000 μg / l or even 400 μg / l or even 0 to 100 μg / l.
Die Erfinder haben erkannt, dass eine wesentliche Verbesserung bezüglich des Restgehaltes an spezifikationsschädlichen Komponenten, insbesondere Kationen, im ADG möglich ist, wenn in der Zuleitung des Diethylenglykols zum Reaktor ein Hochleistungsfilter eingebaut wird, der zur Abscheidung von Feststoffpartikeln mit einer maximalen Partikelgröße <1 ,5 μm, bevorzugt mit einer maximalen Partikelgröße < 1 μm, geeignet ist.The inventors have recognized that a significant improvement in the residual content of components harmful to specifications, in particular cations, in the ADG is possible if a high-performance filter is installed in the feed line of the diethylene glycol to the reactor, which is used to separate solid particles having a maximum particle size <1.5 μm, preferably with a maximum particle size <1 μm, is suitable.
Besonders bevorzugt wird ein Filter, dessen Abscheideverhalten sich durch folgende Kennwerte charakterisieren lässt:Particularly preferred is a filter whose separation behavior can be characterized by the following characteristic values:
Für Feststoffpartikel mit einer maximalen Partikelgröße von 0,2 μm wird ein Abscheidegrad von mindestens 60 % erreicht, für Feststoff partikel mit einer maximalen Parti- kelgröße von 0,6 μm ein Abscheidegrad von mindestens 90 %, für Feststoffpartikel mit einer maximalen Partikelgröße von 0,8 μm ein Abscheidegrad von mindestens 95 %, für Feststoffpartikel mit einer maximalen Partikelgröße von 1 ,5 μm ein Abscheidegrad von mindestens 99 % und für Feststoffpartikel mit einer maximalen Partikelgröße von 5,0 μm ein Abscheidegrad von mindestens 99,98 %. Um das Abscheideverhalten zu charakterisieren, lässt sich die maximale Partikelgröße zum Beispiel mittels statischer Lichtstreuung bestimmen.For solid particles with a maximum particle size of 0.2 μm, a separation efficiency of at least 60% is achieved, for solid particles with a maximum particle size of 0.6 μm a separation efficiency of at least 90%, for solid particles with a maximum particle size of 0, 8 μm a degree of separation of at least 95%, for solid particles with a maximum particle size of 1, 5 μm a separation efficiency of at least 99% and for solid particles with a maximum particle size of 5.0 μm a separation efficiency of at least 99.98%. To characterize the deposition behavior, the maximum particle size can be determined, for example, by means of static light scattering.
Bevorzugt wird als Filter ein Beutelfilter aus Polypropylen, insbesondere mit einem Vo- lumen von 30 bis 40 I, insbesondere von 32 I, der in einem Abscheidebehälter eingesetzt und von oben nach unten durchströmt wird. Die Zurückhaltung der Verunreinigungen erfolgt an der Innenseite des Filters.The preferred filter is a bag filter made of polypropylene, in particular with a volume of 30 to 40 l, in particular 32 l, which is used in a separating vessel and flows through from top to bottom. The retention of the impurities takes place on the inside of the filter.
In einer bevorzugten Verfahrensführung werden neben der Filtration des der Synthese zugeführten Eduktes Diethylenglykol auch besondere Betriebsbedingungen in der zur ADG-Reindestillation eingesetzten Kolonne gewählt, die am Ende der Prozesskette angeordnet ist. In dieser Kolonne wird das aufdestillierte ADG in Elektronik-Qualität in flüssigem Zustand als Seitenstrom abgetrennt, während die organischen Nebenkomponenten mit einem Siedepunkt > 235°C (bei 1 ,013 bar) im Sumpf und die organischen Verbindungen mit einem Siedepunkt < 222°C (bei 1 ,013 bar) über Kopf der Kolonne ausgeschleust werden. Die Kolonne wird bevorzugt bei einem Druck von 0,005 bis 0,2 bar betrieben.In a preferred method, in addition to the filtration of the educt diethylene glycol fed to the synthesis, special operating conditions are also selected in the column used for ADG purification by distillation, which is arranged at the end of the process chain. In this column, the distilled ADG is separated in electronic quality in the liquid state as a side stream, while the organic secondary components having a boiling point> 235 ° C (at 1, 013 bar) in the bottom and the organic compounds having a boiling point <222 ° C ( at 1, 013 bar) are discharged from the top of the column. The column is preferably operated at a pressure of 0.005 to 0.2 bar.
Die Zulaufstelle des ADG-haltigen Stromes befindet sich - bezogen auf die theoreti- sehen Trennstufen - oberhalb der Kolonnenmitte. Der gegenüberliegende flüssige Seitenabzug des Reinproduktes befindet sich 1 bis 30, in besonderen Fällen 10 bis 25 theoretische Trennstufen oberhalb der Zulaufstelle im Verstärkungsteil der Kolonne.The feed point of the ADG-containing stream is - based on the theoretical separation stages - above the middle of the column. The opposite liquid side draw of the pure product is 1 to 30, in special cases 10 to 25 theoretical plates above the feed point in the enrichment section of the column.
Bei dem erfindungsgemäßen Verfahren werden die Trennstufen, die sich zwischen dem Zulauf des Roh-ADG-Stromes und dem Abzug des Seitenstromes, enthaltend ADG in Elektronik-Qualität, befinden, gegenüber bekannten Verfahren, bevorzugt mit erhöhter Flüssigkeitsbelastung wL betrieben (bei ansonsten gleich bleibender Geschwindigkeit des aufsteigenden Dampfes). Die Flüssigkeitsbelastung wL stellt das Verhältnis zwischen dem Volumenstrom der auf die Trennstufen herabrieselnden Flüs- sigkeit VL und der freien Querschnittsfläche A der Trennstufen dar. Die Flüssigkeitsbelastung wL besitzt die Dimension einer GeschwindigkeitIn the method according to the invention, the separation stages, which are between the feed of the raw ADG stream and the withdrawal of the side stream containing ADG in electronic quality, compared to known methods, preferably with increased liquid load w L operated (with otherwise constant Speed of rising steam). The liquid load W L represents the ratio between the volume flow of the liquid V L trickling down to the separation stages and the free cross-sectional area A of the separation stages. The liquid load w L has the dimension of a velocity
wL [m/s] = VL [m3 /s] / A[m2 ]w L [m / s] = V L [m 3 / s] / A [m 2 ]
Die Geschwindigkeit des aufsteigenden Dampfes wD wird aus dem Mengenstrom des am Kopf der Kolonne kondensierten Brüden mL , der Dichte des Dampfes pD und der freien Querschnittsfläche A der Trennstufen gebildet: wD[m / s] = mL [kg I s] I pD [kg /m3 ]/ A[m2 ]The velocity of the rising vapor w D is formed from the mass flow of the vapors m L condensed at the top of the column, the density of the vapor p D and the free cross-sectional area A of the separation stages: w D [m / s] = m L [kg I s] I p D [kg / m 3 ] / A [m 2 ]
Bei dem erfindungsgemäßen Verfahren konnten die im Edukt der Produktionsanlagen eingetragenen und am Zulauf der Reinkolonne noch in höheren Anteilen vorhandenen metallischen Verunreinigungen bei einem erhöhten Verhältnis von Flüssigkeitsbelastung wL zu Dampfgeschwindigkeit wD und zwar bevorzugt vonIn the process according to the invention, the metallic impurities introduced in the educt of the production plants and present at the feed of the pure column in relatively high proportions could be at an increased ratio of liquid load w L to steam velocity w D , preferably from
Wu/ wD > 0,160, in besonderen Fällen von wL / wD > 0,170, vom Produkt ferngehalten werden.Wu / w D > 0.160, in special cases of w L / w D > 0.170, be kept away from the product.
Besonders bevorzugt wird das Verfahren mit Rückführung betrieben:The process is particularly preferably operated with recirculation:
Dabei wird das im Prozess nicht zu Wertprodukt umgesetzte Diethylenglykol im Sumpf der ADG-Reinkolonne abgezogen und dem frischen Eduktstrom, enthaltend Roh-ADG, vor dem Filter zugemischt. Diese Verfahrensschaltung ermöglicht eine erhöhte Ausschleusung von metallischen Verunreinigungen, insbesondere nach Abstellungen der Anlage, bei denen durch das Öffnen von Anlagenkomponenten zusätzliche Verunreinigungen in das ansonsten geschlossene System eingetragen werden.In this process, the diethylene glycol which has not been converted into a product of value in the process is withdrawn from the bottoms of the ADG pure column and mixed with the fresh starting material stream containing crude ADG in front of the filter. This process circuit allows an increased discharge of metallic contaminants, especially after shutdown of the system, in which additional impurities are entered into the otherwise closed system by opening system components.
Ausführungsbeispieleembodiments
Das erfindungsgemäße Verfahren wurde unter den genannten Bedingungen in kontinuierlicher Fahrweise in einer Produktionsanlage eingesetzt.The inventive method was used under the conditions mentioned in continuous operation in a production plant.
Es wurde eine ADG-Reinkolonne mit 44 theoretischen Trennstufen eingesetzt, wobei zwischen der Zuführung des Eduktstromes, enthaltend Roh-ADG, und dem Abzug des Seitenstromes, enthaltend Rein-ADG in Elektronik-Qualität, 9 theoretische Trennstufen angeordnet waren. Es wurde das Verhältnis von Flüssigkeitsbelastung und Dampfgeschwindigkeit für die theoretischen Trennstufen zwischen der Zuführung des Eduktstroms und dem Abzug des Seitenstromes variiert und dessen Einfluss sowie der Einfluss des Einsatzes eines Filters im Eduktweg auf die Eisen-Restkonzentration im Produkt untersucht.An ADG-pure column with 44 theoretical plates was used, whereby 9 theoretical plates were arranged between the supply of the starting material stream, containing crude ADG, and the withdrawal of the side stream, containing pure ADG in electronic quality. The ratio of liquid loading and vapor velocity was varied for the theoretical plates between the feed of the reactant stream and the withdrawal of the side stream and its influence and the influence of the use of a filter in Eduktweg on the residual iron concentration in the product examined.
Beispiele 1 bis 3Examples 1 to 3
Es wurde ein Eduktstrom enthaltend Diethylenglykol mit 300 ppb Eisen eingesetzt. Beispiel 1An educt stream containing diethylene glycol with 300 ppb of iron was used. example 1
Das Verhältnis von Flüssigkeitsbelastung und Dampfgeschwindigkeit wurde auf einen Wert von 0,165 eingestellt. Das Verfahren wurde ohne mechanischen Filter im Edukt- weg betrieben.The ratio of liquid load to vapor velocity was set to a value of 0.165. The process was operated without mechanical filter in the educt path.
Der Produktstrom, enthaltend Rein-ADG, hatte eine Eisenkonzentration von 50 ppb.The product stream containing pure ADG had an iron concentration of 50 ppb.
Beispiel 2Example 2
Das Verfahren wurde analog Beispiel 1 , ebenfalls ohne mechanischen Filter im Edukt- weg, jedoch mit einem Verhältnis von Flüssigkeitsbelastung zu Dampfgeschwindigkeit von 0,185, betrieben.The process was carried out analogously to Example 1, likewise without mechanical filter in the educt path, but with a ratio of liquid load to vapor velocity of 0.185.
Die Eisen-Restkonzentration im ADG-Produktstrom betrug 27 ppb.The residual iron concentration in the ADG product stream was 27 ppb.
Beispiel 3Example 3
Das Verfahren wurde analog Beispiel 1 und 2 betrieben, jedoch mit einem Verhältnis von Flüssigkeitsbelastung zu Dampfgeschwindigkeit von 0,183, zusätzlich mit einem mechanischen Hochleistungsfilter im Eduktweg, und zwar einem Beutelfilter aus Polypropylen mit einem Volumen von 32 I mit der folgenden Abscheidecharakteristik:The process was operated analogously to Examples 1 and 2, but with a ratio of liquid load to vapor velocity of 0.183, in addition to a high performance mechanical filter in the educt path, namely a polypropylene 32L bag filter having the following separation characteristics:
für Feststoffpartikel mit einer maximalen Partikelgröße von 0,2 μm ein Abscheidegrad von mindestens 60 %, für Feststoffpartikel mit einer maximalen Partikelgröße von 0,6 μm ein Abscheidegrad von 90 %, für Feststoffpartikel mit einer maximalen Partikelgröße von 0,8 μm ein Abscheidegrad von mindestens 95 %, für Feststoffpartikel mit einer maximalen Partikelgröße von 1 ,5 μm ein Abscheidegrad von mindestens 99 % und für Feststoffpartikel mit einer maximalen Partikelgröße von 5,0 μm ein Abschei- degrad von mindestens 99,98 %.For solids with a maximum particle size of 0.2 μm, a separation efficiency of at least 60%, for solid particles with a maximum particle size of 0.6 μm a separation efficiency of 90%, for solid particles with a maximum particle size of 0.8 μm a separation efficiency of at least 95%, for solid particles with a maximum particle size of 1.5 μm, a separation efficiency of at least 99% and for solid particles with a maximum particle size of 5.0 μm a separation rate of at least 99.98%.
Die Konzentration an Eisen im Rein-ADG betrug in diesem Fall 9 ppb.The concentration of iron in the pure ADG in this case was 9 ppb.
Beispiele 4 bis 6Examples 4 to 6
Die Beispiele 4 bis 6 wurden mit einer Eisenkonzentration im Eduktstrom von 345 ppb durchgeführt. In sämtlichen Beispielen 4 bis 6 wurde jeweils ein mechanischer Hochleistungsfilter im Eduktweg, entsprechend der Beschreibung zum vorstehenden Beispiel 3, eingesetzt. Die Beispiele 4 bis 6 unterscheiden sich durch unterschiedliche Werte für das Verhältnis aus Flüssigkeitsbelastung und Dampfgeschwindigkeit bei ansonsten unveränderten BetriebsbedingungenExamples 4 to 6 were carried out with an iron concentration in the reactant stream of 345 ppb. In each of Examples 4 to 6, a mechanical high-performance filter in the educt path, as described in Example 3 above, was used in each case. Examples 4 to 6 differ by different values for the ratio of liquid load and steam velocity with otherwise unchanged operating conditions
Beispiel 4Example 4
Das Verhältnis von Flüssigkeitsbelastung zu Dampfgeschwindigkeit betrug 0,178. Dabei wurde eine Restkonzentration an Eisen im Rein-ADG von 7 ppb erzielt.The ratio of liquid load to vapor velocity was 0.178. A residual iron concentration in the pure ADG of 7 ppb was achieved.
Beispiel 5Example 5
Das Verhältnis von Flüssigkeitsbelastung und Dampfgeschwindigkeit betrug 0,155, entsprechend der Betriebsweise nach dem Stand der Technik. Durch Einsatz des Hochleistungsfilters im Eduktweg konnte dabei die Restverunreinigung an Eisen im Rein-ADG auf 28 ppb begrenzt werden.The ratio of liquid load to vapor velocity was 0.155, according to the prior art operation. By using the high-performance filter in the educt path, it was possible to limit the residual iron contamination in the pure ADG to 28 ppb.
Beispiel 6Example 6
Das Verhältnis von Flüssigkeitsbelastung zu Dampfgeschwindigkeit wurde zu 0,175 eingestellt. Die Restverunreinigung im Rein-ADG-Strom an Eisen betrug 8 ppb. The ratio of liquid load to vapor velocity was set at 0.175. The residual contamination in the pure ADG stream of iron was 8 ppb.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von 2,2'-Aminoethoxyethanol in Elektronik-Qualität durch Umsetzung von Diethylenglykol mit Ammoniak in einem Reaktor in Ge- genwart eines Katalysators unter Erhalt eines Reaktionsgemisches, woraus ein1. A process for the preparation of electronics grade 2,2'-aminoethoxyethanol by reacting diethylene glycol with ammonia in a reactor in the presence of a catalyst to give a reaction mixture, of which
Roh-2,2'-Aminoethoxyethanol-Strom abtrennt wird, der in einer Reinkolonne weiter destillativ gereinigt wird, dadurch gekennzeichnet, dass aus der Reinkolonne ein Seitenstrom abgezogen wird, enthaltend 2,2'-Aminoethoxyethanol in Elektronik-Qualität, indem das Diethylenglykol vor der Zuführung desselben zum Reak- tor über einen Filter geleitet wird, der für Feststoffpartikel mit einer maximalenIs separated off crude 2,2'-Aminoethoxyethanol-stream, which is further purified by distillation in a pure column, characterized in that a side stream is withdrawn from the pure column containing 2,2'-aminoethoxyethanol in electronics quality by the diethylene glycol before the feed of the same is passed to the reactor via a filter which is suitable for solid particles with a maximum
Partikelgröße von < 1 ,5 μm einen Abscheidegrad von mindestens 99 % gewährleistet.Particle size of <1, 5 microns ensures a separation efficiency of at least 99%.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das Diethylenglykol über einen Filter geleitet wird, der für Feststoffpartikel mit einer maximalen Partikelgröße von < 1 ,0 μm einen Abscheidegrad von mindestens 99 % gewährleistet.2. The method according to claim 1, characterized in that the diethylene glycol is passed through a filter which ensures a degree of separation of at least 99% for solid particles having a maximum particle size of <1, 0 microns.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Filter ein Beutelfilter aus Polypropylen ist.3. The method according to claim 1 or 2, characterized in that the filter is a bag filter made of polypropylene.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Abzug des Seitenstromes aus der Reinkolonne, enthaltend 2,2'-Amino- ethoxyethanol in Elektronik-Qualität, 1 bis 30, insbesondere 15 bis 25 theoretische Trennstufen oberhalb der Zulaufstelle für den Roh-2,2'-Amino- ethoxyethanolstrom angeordnet ist, und dass die Trennstufen, die sich zwischen dem Zulauf des Roh-2,2'-Aminoethoxyethanolstromes und dem Abzug des Seitenstromes, enthaltend 2,2'-Aminoethoxyethanol in Elektronik-Qualität, befinden, mit einem Verhältnis von Flüssigkeitsbelastung zu Dampfgeschwindigkeit > 0,160, betrieben werden.4. The method according to any one of claims 1 to 3, characterized in that the withdrawal of the sidestream from the pure column, containing 2,2'-aminoethoxyethanol in electronics quality, 1 to 30, in particular 15 to 25 theoretical plates above the feed point is arranged for the crude 2,2'-aminoethoxyethanol stream, and that the separation stages which occur between the feed of the crude 2,2'-aminoethoxyethanol stream and the withdrawal of the side stream comprising 2,2'-aminoethoxyethanol in electronic Quality, are operated with a ratio of liquid load to vapor velocity> 0.160.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass der Abzug des Seitenstromes aus der Reinkolonne, enthaltend 2,2'-Aminoethoxyethanol in Elektronik-Qualität, 1 bis 30, insbesondere 15 bis 25 theoretische Trennstufen oberhalb der Zulaufstelle für den Roh-2,2'-Aminoethoxyethanolstrom angeordnet ist, und dass die Trennstufen, die sich zwischen dem Zulauf des Roh-2,2'-Amino- ethoxyethanolstromes und dem Abzug des Seitenstromes, enthaltend 2,2'- Aminoethoxyethanol in Elektronik-Qualität, befinden, mit einem Verhältnis von Flüssigkeitsbelastung zu Dampfgeschwindigkeit > 0,170 betrieben werden. 5. The method according to claim 4, characterized in that the withdrawal of the side stream from the pure column containing 2,2'-aminoethoxyethanol in electronics quality, 1 to 30, in particular 15 to 25 theoretical plates above the feed point for the crude 2, 2'-Aminoethoxyethanolstrom is arranged, and that the separation stages, which are between the feed of the crude 2,2'-Aminoethoxyethanolstromes and the deduction of the side stream containing 2,2'-aminoethoxyethanol in electronic quality, with a Ratio of liquid load to vapor velocity> 0.170.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Sumpfstrom aus ADG-Reinkolonne abgezogen und dem frischen Eduktstrom, enthaltend Roh-2,2'-Aminoethoxyethanol, vor dem Filter zugemischt wird. 6. The method according to any one of claims 1 to 5, characterized in that the bottom stream withdrawn from ADG-pure column and the fresh reactant stream containing crude 2,2'-aminoethoxyethanol, is added before the filter.
EP07820444A 2006-09-28 2007-09-21 Method for producing electronic grade 2,2'-aminoethoxyethanol Active EP2077989B1 (en)

Priority Applications (1)

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EP06121405 2006-09-28
EP07820444A EP2077989B1 (en) 2006-09-28 2007-09-21 Method for producing electronic grade 2,2'-aminoethoxyethanol
PCT/EP2007/060017 WO2008037659A1 (en) 2006-09-28 2007-09-21 Method for producing electronic grade 2,2'-aminoethoxyethanol

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EP2077989B1 (en) 2012-02-01
CN101528665A (en) 2009-09-09
ATE543794T1 (en) 2012-02-15
JP5260527B2 (en) 2013-08-14
US20100029989A1 (en) 2010-02-04

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